Polystyrene foam extrusion

ABSTRACT

Polystyrene foam is extruded upwardly as a tube into a cooling media of boiling water, both the interior and exterior surfaces of the cylindrically shaped extrudate passing through a bath of boiling water of variable depth. The polystyrene foam extrudate produced by such a method has a high density at the interior and exterior surfaces, with the density progressively decreasing from these surfaces toward the center core of the extrudate.

This is a division of application Ser. No. 526,015, filed Nov. 21, 1974now U.S. Pat. No. 4,009,876, which was a divisional of Ser. No. 394,039,filed Sept. 4, 1973, now U.S. Pat. No. 3,864,444, which issued Feb. 4,1975.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention concerns the upward extrusion of polystyrene foam into acooling media of boiling water. More specifically this invention dealswith a means to form a density gradient from high density interior andexterior surfaces of a tubularly shaped extrudate to a low densitycenter core of the extrudate, thereby increasing the strength andrigidity of the polystyrene foam product.

2. Description of the Prior Art

It has been long recognized that the mechanical properties of certainorganic polymers, such as synthetic long chain polymers, can besubstantially improved by subjecting such polymeric material to adrawing operation, at suitable temperatures, whereby the molecules ofthe polymer are oriented in the direction or directions in which theelongation is applied.

It has been previously proposed to produce molecularly oriented sheetmaterial by extruding a hot ribbon of thermoplastic polymer andstretching the extruded ribbon simultaneously or sequentially, in boththe longitudinal and the transverse directions. See for example U.S.Pat. Nos. 3,055,048 (Koppehele) and 3,676,539 (Fisher). Conventionally,biaxially orienting plastic film has involved the engagement of theedges of the sheet material by stretching devices which are intended tostretch the sheets in the two directions. However, such devices aresomewhat less desirable when utilized to stretch normally brittlethermoplastic material such as polystyrene and polystyrene foam.Polymers of polystyrene are quite brittle at room temperature, and mayfracture when subjected to an external force. In stretching polystyrenesheets, the edges of the thermoplastic material are engaged by grippingmeans which secure the material during the stretching process. Thelocalized stresses created at the point of engagement, particularlywhere the gripping means are at a temperature lower than that of thethermoplastic material, are often sufficient to produce fractures of thematerial. Such fractures are particularly prevelant where thethermoplastic material is brittle such as is the case with polystyrenefoam.

Work in recent years has accordingly been performed in the developmentof methods whereby the mechanical properties of thermoplastic materialssuch as polystyrene foam might be improved through biaxial orientationwithout the use of such stretching devices. U.S. Pat. No. 2,987,776(Miller) is an example of such a process. That patent discloses a methodwhereby a liquid and gas mixture is injected into the hollow interior ofa tubular film extrudate as it is being externally cooled. Themechanical properties of such a thermoplastic material may beadditionally toughened by processes which further improve upon thestrength increase derived from orienting the thermoplastic materialmolecules.

U.S. Pat. No. 3,299,192 (Lux) states that the rigidity, liquid handling,and thermal insulation capability of foamed plastic pipe was enhanced byquench chilling the internal and exterior walls of the tube within ashort time after it emerged from an extrusion die. The patent notes thatsuch chilling produces an impervious and non-porous (so as to promoteliquid handling) internal and external skin on the pipe. The patentnotes that the inner skin might be made 2 to 5 times as thick as theouter skin for purposes of carrying liquids such as water. Thedisclosure suggested coolant temperatures of 0° to 80° F and velocitiesof 50 to 100 ft/sec. The examples recite the use of 70° F air as acoolant, blasted from a nozzle upon the extrudate surfaces. Suchchilling produced a pipe having a core representing 50 to 94% of thethickness of the pipe, the interior and exterior skins representing thebalance of the pipe thickness.

The present invention while related to the Miller and Lux patentsdistinguishes from them in its ability to very precisely control thecooling conditions of a particular thermoplastic, polystyrene foam, soas to greatly enhance that materials' strength properties. The presentinvention utilizes the unusual properties of a particular coolant toproduce a unique polystyrene foam extrudate having a density gradient ofdecreasing value from the outside surface to the core.

It is an object of this invention to provide a means for the productionof a polystyrene foam extrudate wherein the temperature of the coolingfluid, and thus the cooled extrudate may be very precisely controlled.

A further object of this invention is to provide means capable ofprecisely controlling a temperature gradient across a thickness ofpolystyrene foam extrudate.

An object of this invention is to cool from both the interior andexterior surfaces a polystyrene foam extrudate at a precise temperatureselected from the range of about 15° to 55° F above its glass transitionpoint.

Another object of this invention is to inhibit polystyrene foam cellgrowth in such a manner as to produce an extrudate whose density andcorresponding strength across an extrudate cross section areproportional to the tension and compression stresses which would beproduced across such an extrudate cross section when such an extrudatehas a moment applied at its end point.

A further object of this invention is to provide means capable ofvarying the degree of change (or slope) in density across a polystyrenefoam extrudate.

Another object of this invention is to provide means to vary the time apolystyrene extrudate is cooled in a coolant bath without varying therate at which polystyrene is extruded from an extension die.

Other additional objects of this invention will become apparent upon aconsideration of this entire specification including the drawing andclaims.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a cross section view of a polystyrene foam extrudate which hasbeen modified in accordance with this invention.

FIG. 2 represents a cross sectional view of an apparatus adopted toperform the method of this invention.

FIG. 3 represents a comparison of the strength of various members as afunction of density.

SUMMARY OF THE INVENTION

When a product produced from a thermoplastic material which isreasonably long compared with its lateral dimensions so as to resemble abeam is subjected to an external force which produces a moment M, thestress σ produced at any point P in the material may be expressed asfollows:

    σ = My/I

where I represents the moment of inertia of the material and y is thedistance of a point P from the neutral surface of the material. (See,Timoshanko and Young, Strength of Materials 4th ed. (1962) pp. 95-133).

Thus for a material having a given moment of inertia and applied moment,the stresses in the material vary depending upon where point P islocated. At the neutral surface, the stresses are zero as y is zero. Asy increases, as one moves away from the neutral axis, the stressesincrease proportionally. The maximum stresses thus occur at the surfacesof a homogenous material since these surfaces are farthest from theneutral surface.

A consideration of the previously referenced equation leads one to theconclusion that the most economical design would allow for the bulk ofthe member strength to be located as far away from the neutral axis aspossible, so as to be more able to withstand the higher stresses whichexist farther away from the neutral surface. Such considerations led tothe development of I beams in the structural steel area.

Such a design would aid in preventing a common failure of broken cornersexperienced in polystyrene foam trays such as meat trays utilized topackage and display meats and other products. Such corner breakstypically occur from bending produced due to the weight of the articleon the tray when the tray is held by the corner at which failure occurs.The breaks generally occur due to a crack which forms at the surface ofthe tray, due to the high stress at the surface fibers, the crack thenpropagating through the tray thereby producing a broken or fracturedcorner section.

Moreover, the density of the interior portion of such a design, ascontrasted with the almost crystalline density of the exterior, producesa resillant and flexible inner section. Such a section partially absorbsthe stresses produced by bending, thus further aiding in the preventionof foam tray broken corners.

The present process for producing such an improved product employs acombination of the unique properties of polystyrene and water, andproduces a product having greater strength at the polystyrene foamsurface where bending stresses are greatest.

According to the present invention, molten polystyrene upon emergingfrom an extruder die orfice is immediately contacted with boiling waterat a temperature selected from the range of about 170° - 230° F. Suchtemperatures may be achieved by varying the pressure of the boilingwater reservoir from which the boiling water is circulated to thepolystyrene cooling chamber and then returned to the reservoir. Suchpressure might be controlled for example by varying the hydraulic headwithin the reservoir. The reservoir could also be placed under a vacuumfor lower boiling temperature. Perhaps due to the fact that suchtemperatures are slightly above the glass transition point or softeningpoint of polystyrene (about 175° F), boiling water has not previouslybeen considered as a cooling media for polystyrene foam extrudate.However, it has been discovered that the use of boiling water to coolthe extrudate produces unusually superior results. The uniquecharacteristics of water at its boiling point allow for very precisecontrol of the strength properties of polystyrene product produced. Theextremely high heat of vaporization of water (about 977 B.T.U./lb at212° F) allows for very exact temperature control at the water boilingpoint. Water will absorb great quantities of heat before forming steamat a temperature above the water boiling temperature. It has beencalculated that the heat absorption of one pint of boiling water(without changing temperature) is equivalent to the heat absorptioncapabilities of about 13,000 cubic feet of air with a 4.5° F temperaturechange. The heat absorptive capabilities of water thus allow for greatlyreduced coolant velocities. In a preferred embodiment the boiling watercoolant is circulated at a rate of about 0.25 lbs/min. to about 5lbs/min.

The relatively high temperature of the boiling water coolant allows formore precise control of the polystyrene extrudate temperature becausethe small temperature differential between the coolant and thepolystyrene (typically extruded at about 270° to 320° F) allows thecooling to take place slowly and gradually at the core. Moreover, thisinvention's apparatus for carrying out the process allows for varying ofthe time the extrudate is exposed to the boiling water through varyingthe height of the water bath through which the extrudate is passed.

In addition to the high heat of vaporization characteristic of water at212°0 F, the design of the invention's apparatus for cooling thepolystyrene extrudate allows for utilization of the steam condensateproduced by the process as a lubricant for the polystyrene being formed.

The polystyrene article produced when cooled in accordance to the methodof the invention has a density gradient from the center core of thearticle to the surface of the article. The density of the surfaces has adensity range of about 65 to about 55 lb/ft³, while the center core hasa density of about 1.3 to about 3 lb/ft³. The core represents at least95% of the thickness of the article, and it represents about 97% in apreferred embodiment.

Various polymers can be used to form the foamed plastic sheeting.

Although elongation to a substantial extent negates the need for arubber additive, it is anticipated that such an additive might beutilized in connection with this process. When employing polystyrenethere can be employed normal crystal grade polystyrene or high impactpolystyrene or a mixture containing 5 to 95% normal crystal gradepolystyrene and the balance high impact polystyreme. High impactpolystyrenes are frequently prepared by polymerizing monomeric styrenein the presence of 21/2 to 10% weight of a rubbery diene polymer or bypolymerizing styrene in the presence of such amounts of a difunctionalmaterial. (Unless otherwise indicated, all parts and percentages are byweight).

To insure the formation of a foamed plastic core, a nucleating agentshould be used in forming the foamed sheet. When a nucleating agent isemployed, it is used in an amount of from 0.02 to 10% of the totalpolystyrene by weight. Preferably, 0.2 to 2% of the nucleating agent isused.

Conventionally, the nucleating agents are made up of two materials whichreact to form carbon dioxide and water. The two materials are normallyused in approximately equivalent amounts. As the carbon dioxideliberating materials there can used ammonium, alkali and alkaline earthcarbonates or bicarbonates, e.g., ammonium bicarbonate, sodiumbicarbonate, sodium carbonate, potassium bicarbonate, calcium carbonate.The other material is an acid or acid-reacting salt, preferably solid,which is sufficiently strong to liberate the carbon dioxide from thecarbonate or bicarobonate. Generally, the acid has at least 3.0milliequivalents of acidic hydrogen, and preferably at least 10.0milliequivalents, per gram. The acid can be organic or inorganic.Suitable acidic materials include boric acid, sodium dihydrogenphosphate, fumaric acid, malonic acid, oxalic accid, citric acid,tartaric acid, potassium acid tartrate, chloroacetic acid, maleic acid,succinic acid and phthalic acid. In place of the anhydrous acids orsalts there can be used the solid hydrates, e.g., oxalic acid dihydrateand citric acid monohydrate.

While not essential, there can also be added a wetting agent such asBayol 35 (a petroleum aliphatic hydrocarbon white oil), kerosene havingan average of at least 8 carbon atoms in the molecule,alkylphenolalkylene oxide adducts, e.g., Triton X-100(t-octylphenol-ethylene oxide adduct having 10 ethylene oxide units inthe molecule, sodium lauryl sulfate and sodium dodecylbenzene sulfonate.The wetting agent can be nonionic or anionic.

One mode of incorporating the foaming agent into the polymer is bypremixing the pelletized solid thermoplastic polymer, e.g., a styrenepolymer, with a minor amount of an absorbent having absorbed thereon avolatile liquid (i.e., the foaming agent) which is non-reactive with andwhich has not more than a slight solvent action on the polymer. Theliquid should volatilize below the softening point of the polymer.

The preferred mode entails a dual extrusion process. A pre-blendedmixture of nucleating agent and polystyrene pellets are fed into a firstor primary extruder. A blowing agent is separately injected into theprimary extruder, preferably at about the midpoint of the primaryextruder barrel. This homogenous mixture of polystyrene, nucleating andblowing agent is then passed through a second extruder which is utilizedto control the temperature at which the mixture exits the extrusionsection.

As the absorbent there can be employed any conventional absorbent infinely divided form, such as diatomaceous earth (Celite), fuller'searth, silica gel, e.g., Cab-O-Sil and Hi-Sil, activated alumina,molecular sieves, attapulgus clay and activated carbon. The absorbent isusually used in an amount of 0.1-15%, preferably 0.5 to 10% by weight ofthe polymer, although up to 25 or 30% of absorbent can be employed. Theabsorbent is an inert filler of large surface area but small particlesize, e.g., 200 mesh or below.

As the volatile liquid there can be used aliphatic hydrocarbons boilingbetween 10° and 100° C. and preferably between 30° and 90° C., e.g.,petroleum ether (containing primarily pentane or hexane or a mixture ofthese hydrocarbons), pentane, hexane, isopentane, cyclohexane,cyclopentane, pentadiene and neopentane. Other volatile liquids includemethanol, ethanol, methyl acetate, ethyl acetate, butane, acetone,methyl formate, ethyl formate, dichloroethylene, perchloroethylene,dichlorotetrafluoroethane, isopropyl chloride, propionaldehyde,diisopropyl ether, dichlorodifluoromethane, a mixture of pentane with 5to 30% of methylene chloride or other volatile lower halogenatedhydrocarbon.

The amount of volatile liquid absorbed on the absorbent can vary from 5to 150% or more based on the weight of the absorbent. The amount ofliquid absorbed will depend upon the capacity of the absorbent for theparticular liquid. Normally, the absorbent containing the volatileliquid will appear to be a dry powder. The volatile liquid employedshould be one which is non-reactive with the particular polymeremployed. Usually, the amount of volatile liquid will be 0.1 to 15% byweight of the polystyrene to be expanded. The amount of volatile liquidwill depend upon the extent of the foaming desired. In general, thegreater the amount of absorbed volatile liquid in the polymer-absorbentmixture the more the expansion. It has been found that good expansioncan be obtained using very small amount of the volatile liquid.

The volatile liquid is held in solution with the molten polystyrene bythe pressure which is used to force the mixture of polystyrene,nucleating agent and volatile liquid (sometimes referred to as a blowingagent) through the extrusion die. Upon leaving the extrusion die orfice,the volatile liquid begins to expand (due to the decreased pressure andthe high molten polystyrene temperature) and form a cell structurereferred to as foam. The cooling provided by the boiling water inhibitscell growth as the lower temperature produced by boiling water inhibitsthe volatile liquid expansion. It has been found that the amount of thecells making up the foam structure form a gradient similar to thetemperature gradient across a cross-section of polystyrene. Therelatively hot core produces most of the cells, and the number of thecells decreases (proportional to the temperature decrease) from thiscenter core outward toward the interior and exterior surfaces of thecylindrical extrudate. As the number of the cells decreases, the densityand strength of the polystyrene foam extrudate increases. Production ofsuch a density gradient allows for the production of polystyreneproducts whose average density is less for a given strength thanpolystyrene products without such a density gradient.

Polystyrene products having a uniform cross-section (no densitygradient) must have a density at the outer surface, where the greatestcompressive and tensional forces due to bending occur, sufficient towithstand such compressive and tensional forces. Thus the density of theentire cross-section of the product would be determined by the densityand strength requirements of the interior and exterior surface fibers.

Application of the present invention allows for very exact tailoring ofthe polystyrene density and corresponding strength. FIG. 3 illustratesthe dramatic average foam density decreases which may be achieved byapplicant's method with not only no resulting loss in strength, but infact a strength increase. The three curves of FIG. 3 all show thestrength of polystyrene members such as trays utilized to display andsupport products such as meat in supermarkets and other retail outlets.The strength is plotted against the average density of the polystyreneproduct in the curves of FIG. 3. Curve 1 shows the strengthcharacteristics of a constant density foam (no density gradient throughthe polystyrene thickness). Curve 2 illustrates a polystyrene foamproduct of varying densities (as shown) having a constant 0.5 miloriented skin on both sides of its core. Curve 3 shows the beam strengthproperties of a polystyrene foam product having a constant core densityand varying skin thickness (as shown). While curves 2 and 3 do notrepresent true gradients they do approximate such gradients andillustrate the dramatic strength increases which may be produced by moreclosely matching density to stresses produced by bending. Examination ofthe curves shows that a foam gradient product having an average densityof 2.6 lb/ft.³ produces a beam strength 2.6 times as great as that of aproduct having a constant density of 4.3 lb/ft.3

The economic importance of such an invention is clear. Polystyreneproducts may be produced which require less than half the amount ofpolystyrene presently used, yet which have greater strength properties.Production line speeds might be increased 100% without changing theamount of molten polystyrene flow through the extruder.

DESCRIPTION OF SPECIFIC EMBODIMENTS

Referring to FIG. 1, an article, such as a tray produced frompolystyrene foam, 1 is supported or held at each end 3 and 2, the weightof a product or substance on the tray 1 produced a force F, which tendsto deflect or bow a middle portion 6 of the tray 1 downward. The force Falso produces a movement M at the end 2 of tray 1. The defection isexaggerated in FIG. 1 for purposes of illustration. A top portion 12 ofthe tray 1 is placed in compression due to the downward deflection ofthe middle portion 6 produced by force F while the bottom portion 14 isplaced in tension.

The top portion 12 of the tray 1 tends to shorten due to the compressionforces, while the bottom portion 14 tends to elongate due to the tensionforces. Somewhere in between the top portion 12 and the bottom portion14, there is a surface shown as a surface 13 in FIG. 1, which remainsunchanged in length and is termed a neutral surface.

Referring to the equation noted, the stresses vary linearly with thedistance from the neutral surface 13. Thus the greatest stresses of thematerial fibers occur at the top surface 12 and the bottom surface 14 asthese surfaces are the farthest removed from the neutral surface 13. Formaterials which are homogeneous and obey Hooke's law, the modulus ofelasticity in tension is the same as that in compression, and thestresses at the top surface 12 and the bottom surface 14 of thepolystyrene article will be equal.

Referring now to FIG. 2, an apparatus and process are described whichmay be used to produce an economically designed material made ofpolystyrene.

Molten polystyrene at a temperature of at least about 280° F is forceddue to pressure into a die 24 by way of an inlet 20. The moltenpolystyrene is forced upwardly through an annular passage 28 of the die24 and emerges as a tubular shaped extrudate 30 from an annular orfice26. Immediately upon exiting from the annular orfice 26, the moltenpolystyrene is contacted with water boiling at 212° F in a chamber 40.The tubularly shaped extrudate 30 is drawn between an annular calenderring inner member 52 and an outer member 54. The inner member 52 andouter member 54 may be chilled with cold water (below 100° F) which iscirculated through a cavity 53 in the inner member 52 and a cavity 55 inthe outer member 54. A knife 62 is mounted on a support 60 in the pathof the tubularly shaped polystyrene extrudate 30 so as to cut throughthe extrudate 30 as the extrudate 30 is drawn across the knife 62.

Of particular novelty is that portion of the extrusion apparatus whereinthe polystyrene extrudate 30 passes through a bath of boiling watercontained in the chamber 40. This portion of the apparatus will now bediscussed in detail.

Boiling water is supplied at a center inlet 42. Water entering inlet 42is forced upward in the annular opeining between a hollow duct 45 and anenclosing hollow duct 43. This boiling water may be discharged at apoint 47 into chamber 40 wherein the interior surface of the polystyreneextrudate 30 is contacted with the water. Water upon reaching the top 50of the vertically adjustable duct 45 passes down the hollow innerportion of the duct 45 and may then be recooled (reheated duringstartup) and reintroduced at an inlet 42 or inlet 44.

The outer surface of the extrudate 30 is cooled in a similar manner.Boiling water may be forced into the outer inlet 44 and passes through ahousing 46 and into the chamber 40 through an annular opening 49. Uponreaching the level of the top of a vertically adjustable hollow duct 54,the water passes down the hollow inner portion of the duct 54 and maythen be recooled (reheated during startup) and reintroduced at outerinlet 44 or inner inlet 42. In a preferred embodiment the coolanttemperature and bath height are the same at the interior and exteriorsurfaces of the extrudate being cooled. However, such temperatures mightbe held at different points and the bath height varied in order toachieve a particular product strength.

Water droplets condense on an upper wall 48 of the chamber 40 as theupper wall 48 is adjacent the cold water circulated in the cavities 53and 55. The wall 48 is sloped so as to allow such condensate to traveldownward along the surface of the wall 48 to an inlet 61 to the calenderring members 52 and 54. Such water condensate acts as a lubricant andfacilitates the passage of the extrudate 30 between the inner calenderring member 52 and the outer calender ring member 54.

What is claimed is:
 1. An integral polystyrene foam extrudate having adensity gradient from the central core of said article to the surfacesof said article; said surfaces having a density of about 65 to about 55lb/ft³ ; and said core having a density of about 1.3 to about 3 lb/ft³,said core representing not less than 95% of the thickness of saidextrudate, said polystyrene foam having been produced in accordance witha method comprising extruding said foamable composition in tubular formdirectly into boiling water maintained at substantially the same height,both inside and outside said tubular extrudate; foaming said extrudatein said boiling water under cooling conditions whereby said tubularextrudate as formed has a density gradient decreasing from the externalsurfaces inwardly.
 2. A product as claimed in claim 1 wherein saidboiling water temperature is within the range of about 170° to 230° F.3. The product as claimed in claim 2 wherein said polystyrene extrudatetemperature is within the range of about 270° to 320° F.
 4. The productas claimed in claim 1 wherein said core represents about 97% of thethickness of said extrudate.